近红外发射荧光材料的研究

近红外发射材料在便携式近红外光谱仪、太阳能电池、光学通信、环境监测等领域有着潜在应用价值.其主要包含掺杂过渡金属离子(如Cr~(3+))、掺杂稀土离子(如Yb~(3+),Eu~(2+))的荧光粉以及半导体量子点(如Ag_2S,PbS).结合以上分类,介绍了近年来近红外发射材料的研究进展.     

稀土氧化物掺杂对TiO2/沸石光催化性能的影响

以钛酸丁酯和稀土氧化物为原料, 采用溶胶 凝胶法制备了镧、 钕和镱稀土离子掺杂TiO₂/沸石光催化剂. 通过XRD和IR方法对样品进行表征, 研究了不同沸石粒径及不同稀土氧化物掺杂量(质量分数)对农药敌敌畏光催化降解性能的影响. 结果表明, 当沸石最佳粒径为0.15 mm, La³⁺掺杂量质量分数为3.0%时（以TiO₂质量计）, 稀土离子的掺杂可显著提高TiO₂//沸石的光催化降解性能.     

Photoluminescence and cathodoluminescence properties of a novel CaLaGa307：Dy3＋ phosphor

A single host white emitting phosphor, CaLaGa3O7:Dy3+, was synthesized by chemical co-precipitation. Field emission scanning electron microscopy, X-ray diffraction, laser particle size analysis, and photoluminescence and cathodoluminescence spectra were used to investigate the structural and optical properties of the phosphor. The phosphor particles were composed of microspheres with a slight tendency to agglomerate, and an average diameter was of about 1.0 μm. The Dy3+ ions acted as luminescent centers, and substituted La3+ ions in the single crystal lattice of CaLaGa3O7 where they were located in Cs sites. Under excitation with ultraviolet light and a low voltage electron beam, the CaLaGa3O7:Dy3+ phosphor exhibited the characteristic emission of Dy3+ (4F9/2-6H15/2 and 4F9/2-6H13/2 transitions) with intense yellow emission at about 573 nm. The chromaticity coordinates for the phosphor were in the white region. The relevant luminescence mechanisms of the phosphor are investigated. This phosphor may be applied in both field emission displays and white light-emitting diodes.     

Synthesis and luminescence properties of Ca2SiO4-based red phosphors with Sm3+ doping for white LEDs

Sm³⁺-activated Ca₂SiO₄ red phosphors were prepared by the conventional high-temperature solid-state reaction method, and the effects of sodium (Na⁺) and samarium (Sm³⁺) ions doping concentrations on their crystal structure and luminescent properties were investigated by X-ray diffraction (XRD) and fluorescent spectrofluorometer. XRD patterns demonstrate that a well-crystalline structure forms in the phosphors when they are treated by calcination at 1200°C for 4 h, and the excitation spectra exhibit good absorption in the range between 350 and 420 nm. Under the irradiation of 405 nm near-ultraviolet (NUV) light, the spectra of the phosphors show a main emission peak at 601 nm attributed to the ⁴G_5/2??⁶H_7/2 transition of Sm³⁺ ions, and its intensity is greatly influenced by the concentrations of Sm³⁺ and Na₂CO₃. When the concentrations of Sm³⁺ ions and Na₂CO₃ are 2mol% and 6mol%, respectively, the optimal emission intensity can be obtained. From strong absorption in the near ultraviolet zone, the Na_0.06Sm_0.02Ca_1.92SiO₄ phosphor is a promising red-emitting phosphor for white light emitting diodes (W-LEDs).     

Novel trichromatic phosphor Co-doped with Eu, Tb in SiO2 gel matrix

The Eu, Tb co-doped SiO2 matrix tricolor fluorescence system was prepared by sol-gel technique. Red emission at 618 nm, green emission at 543 nm and blue emission at 350-500 nm were observed in the PL spectra of the sample, indicating that Eu^3＋, Eu^2＋ and Tb^3＋ ions coexisted in the matrix. In the co-doped sample, the blue emission of Eu^2＋ was much stronger than that of the sample single doped with Eu, which implied that the electron transfer between Eu^3＋ and Tb^3＋ maybe happened in the SiO2 matrix. The influences of the annealing temperature and Tb concentration on the PL spectra of the samples were investigated. The optimal doped concentration of Tb was determined to be 0.2% and the optimal annealing temperature 850℃. Annealed at 600℃, Tb^3＋ had a sensitizing effect on Eu^3＋ in the SiO2 matrix, and the emission intensity of Eu^3＋ in the Eu, Tb co-doped sample was more than four times that of the single doped sample, which could be attributed to the energy transfer from Tb^3＋ to Eu^3＋.     

Preparation and upconversion luminescence of YVO<Subscript>4</Subscript>:Er<Subscript>3+</Subscript>, Yb<Subscript>3+</Subscript>

YVO₄:Er³⁺, Yb³⁺ with varying Yb³⁺ concentrations were prepared by a precipitation method. The results of X-ray diffraction (XRD) show that all the samples have a tetragonal zircon structure; the calculated average crystallite sizes are in the range of 14–22 nm. The lattice constants and cell volume of the samples decrease slightly with the increase in Yb³⁺ concentration. The upconversion luminescence spectra of all the samples were studied under 980 nm laser excitation. The strong green emission is observed, which is attributed to the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2→⁴I_15/2 transitions of Er³⁺, and the red emission peaks in 650–675 nm can be ignored. The emission intensity for the sample depends on the Yb³⁺ concentration. These results reveal that the upconversion processes of YVO₄:Er³⁺, Yb³⁺ are related to the structure and the doping Yb³⁺ concentration of the sample.     

Near-infrared to visible up-conversion emissions of Er^3＋ doped Al2O3 powders derived from the sol-gel method

The Er3 doped Al2O3 powders were prepared by the sol-gel method using the aluminium isopropoxide [Al(OC3H7)3]-derived Al2O3 sols with addition of the erbium nitrate [Er(NO3)3.5H2O]. The different phase structure, including three crystalline types of (Al,Er)2O3 phases, γ, θ, α, and two Er-Al-O phases, ErAlO3 and Al10Er6O24, was obtained with the 1 mol% Er3 doped Al2O3 powders at the different sintering temperatures of 600―1200℃. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the 2H11/2, 4S3/2→4I15/2 and 4F9/2→4I15/2 transitions of Er3 , were detected by a 978 nm semiconductor laser diodes excitation. The phase structure and OH content had evident influence on the up-conversion emissions intensity. The maximum intensities of both the green and red emissions were obtained respectively for the Er3 doped Al2O3 powders sintered at 1200 ℃, which was composed mainly of α-(Al,Er)2O3, less of ErAlO3 and Al10Er6O24 phases, and with the least OH content. The two-photon absorption up-conversion process was involved in the green and red up-conversion emissions of the Er3 doped Al2O3 powders.     

Down-conversion characteristics of Eu3+ doped M2Y2Si2O9 (M = Ba,Ca, Mg and Sr) nanomaterials for innovative solar panels

Down-conversion properties of Eu³⁺ doped M₂Y₂Si₂O₉ (M = Ba, Ca, Mg, Sr) phosphors have been investigated in detail. These phosphors were synthesized via the simple, fast and cost-effective sol-gel technique at a temperature of 950 °C. Color coordinates and emission color can be altered by the varying concentration of dopant ion in Ca₂Y₂Si₂O₉ phosphor. Optimum luminescence intensity was obtained when doping 0.03 mol of Eu³⁺ ion. Using the excitation wavelength of 395 nm, these silicates showed strong red color, pure and sharp spectral peaks in visible region due to ⁵D₀→⁷F_1-3 transitions of Eu³⁺ present in the lattice. Effect of reaction temperature on luminescence was also analyzed for these phosphors. The sharp peaks in the X-ray diffraction pattern indicated the high crystallinity of prepared phosphors. Ca₂Y₂Si₂O₉ has shown an orthorhombic crystal structure. The FTIR results confirmed the metal-oxygen vibrational modes available in the range of 400–1600 cm^?1. Transmission electron microscopy images have revealed that the variation of alkaline earth metal provided a very different crystal structure. Excellent down conversion response of these phosphor materials can provide a great significance in the application of the coming solar devices.     

SrBPO_5中铕和铽的发光

利用Ｅｕ３＋和Ｔｂ３＋的电子组态具有共轭性的原理,在空气中合成了ＳｒＢＰＯ５：Ｅｕ,Ｔｂ荧光体系,研究了其光谱特征,发现Ｅｕ３＋和Ｔｂ３＋和Ｅｕ２＋共存于该体系中,且Ｅｕ２＋的发光强度随Ｔｂ３＋离子浓度的增大而增强．     

Photoluminescence and cathodoluminescence properties of CaLaGa<Subscript>3</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>3+</Superscript> phosphors

The CaLaGa₃O₇:Eu³⁺ phosphor was prepared by a chemical co-precipitation method. Field emission scanning electron microscopy (FE-SEM), laser particle size analysis, X-ray diffraction (XRD), photoluminescence (PL), and cathodoluminescence (CL) spectra were utilized to characterize the synthesized phosphor. The results revealed that the phosphor was composed of microspheres with a slight agglomerate phenomenon and was spherically shaped. The average grain size was about 1.0 μm. Eu³⁺ ions, as luminescent centers, substituted La³⁺ ions into the single crystal lattice of CaLaGa₃O₇ with the sites of C_s. Although the CL spectrum was greatly different from the PL spectrum, it had the strongest red emission corresponding to the ⁵D₀ →⁷F₂ transition of Eu³⁺. Under the excitation of UV light (287 nm) and electron beams (1.0–7.0 kV), the chromaticity coordinates of the phosphor were found to be in the nearly red and orange light regions, respectively.     

Er3+/Yb3+共掺杂的氟氧化物玻璃陶瓷中新的能量传输过程

为了研究铒离子的发光和氟氧化物玻璃中形成的氟化物微晶的关系，制备了三种掺饵的氟氧化物玻璃，用X射线衍射分析了样品中形成的氟化物微晶，从632.8nm激光激发时间的发射光谱中，首次发现了一种新的氟氧化物玻璃基质发光的现象。在氟氧化物玻璃中如果没有形成氟化物微晶，铒掺杂于玻璃中,632.8nm激光激发时激发态的铒离子容易将能量传递给基质并引起基质发光；如果将镱和铒离子共同掺入氟氧化物玻璃中，容易形成含稀土铒镱的氟化物微晶，含微晶的玻璃又叫玻璃陶瓷，由于氟化物的声子能量较小，632.8nm激光激发时激发态的铒离子的无辐射弛豫几率较小，铒离子的发光较强，在玻璃中形成含稀土氟化物微晶可以减小基质的发光强度，这是提高铒离子发光的有效手段之一。     

红色荧光粉YAlO3:Eu3+Cu+的制备和发光特性

研究了化学沉淀法制备YAP:Eu3+Cu+荧光粉,得到适宜工艺参数.用XRD和PL谱分别表征前驱体的晶体结构和荧光粉的荧光特性.前驱体的焙烧温度为1 200℃,焙烧时间为2 h;Eu3+的适宜掺杂浓度为3%,而且在398 nm紫外光激发下荧光粉呈现红色光谱,这是由于Eu3+的4fn电子组态内5D0→7FJ(J=0～4)的跃迁发射,由5D0→7F2的发射特性和发射强度表明Eu3+主要处于非反演对称中心.Cu+增强了YAP:Eu3+的发光强度是因为Cu+→Eu3+之间的能量传递,Cu+对Eu3+有敏化作用.     

Sr2CeO4/Ln3+(Ln=Er,Ho,Tm)的微波合成与荧光性质

首次采用微波法合成了Sr2CeO4/Ln3 (Ln=Er,Ho,Tm)荧光体.研究了样品的荧光性质,并观察到Er3 ,Ho3 ,Tm3 掺杂的Sr2CeO4材料的上转换发光现象.荧光光谱证实,存在基质Sr2CeO4向稀土离子Ln3 的能量传递.     

Mn-ion-enhanced red spectral emission from yttrium aluminum garnet doped cerium phosphor

Mnions were co-doped in yttrium aluminum garnet doped cerium(YAG:Ce) phosphors as a co-activator and host lattice element using the co-precipitation method.These ions broadened the emission spectra of the pure YAG:Ce phosphor,which is caused by the 2E-4A2,5E-5T2 or 1T2-5T2 transition.From our X-ray diffraction results,we observed that Ce3+(1.032 ) was substituted at the Y3+(0.900 ) site,and Mn4+(0.538 ) and Mn3+(0.67 ) were substituted at the Al3+(0.535 ) site.The chromaticity color co-ordinates of YAG:Ce0.06 is(0.203,0.167),and the indices of YAG:Ce0.06,Mn0.04 and YAG:Ce0.06,Mn0.08 are(0.249,0.181) and(0.233,0.194),respectively.The manganese co-doped yttrium aluminum garnet doped cerium blended with the YAG:Ce phosphor showed improved white light emission.     

Preparation and luminescence characteristics of Sr3SiO5：Eu^2＋ phosphor for white LED

The Sr3SiO5：Eu^2＋ phosphor was synthesized by high temperature solid-state reaction. The emission spectrum of Sr3SiO5：Eu^2＋ shows two bands centered at 487 and 575 nm, which well agree with the theoretic values of emission spectrum. The excitation spectrum for 575 nm emission center has several excitation bands at 365, 418, 458 and 473 nm. And the results show that the emission spectrum of Sr3SiO5：Eu^2＋ is influenced by the Eu^2＋ concentration. The relative emission spectra of the white-emitting InGaN-based YAG：Ce^3＋ LED and Sr3SiO5：Eu^2＋ LED were investigated. The results show that the color development of InGaN-based Sr3SiO5：Eu^2＋ is better than that of InGaN-based YAG：Ce^3＋, and the CIE chromaticity of InGaN-based Sr3SiO5：Eu^2＋ is （x=0.348, y=0.326）.     

Micro-arc oxidization fabrication and ethanol sensing performance of Fe-doped TiO<Subscript>2</Subscript> thin films

In-situ pure TiO₂ and Fe-doped TiO₂ thin films were synthesized on Ti plates via the micro-arc oxidation (MAO) technique. The as-fabricated anatase TiO₂ thin film-based conductometric sensors were employed to measure the gas sensitivity to ethanol. The results showed that Fe ions could be easily introduced into the MAO-TiO₂ thin films by adding precursor K₄(FeCN)₆·3H₂O into the Na₃PO₄ electrolyte. The amount of doped Fe ions increased almost linearly with the concentration of K₄(FeCN)₆·3H₂O increasing, eventually affecting the ethanol sensing performances of TiO₂ thin films. It was found that the enhanced sensor signals obtained had an optimal concentration of Fe dopant (1.28at%), by which the maximal gas sensor signal to 1000 ppm ethanol was estimated to be 7.91 at 275°C. The response time was generally reduced by doped Fe ions, which could be ascribed to the increase of oxygen vacancies caused by Fe³⁺ substituting for Ti⁴⁺.     

Y2O2S:Eu3+,Zn2+,Ti4+荧光体的缺陷及红色长余辉发光性质

采用高温固相法合成了红色长余辉材料Y2O2S:Eu3+,Zn2+,Ti4+,实现了余辉发光中心和缺陷中心之间的能量传递。通过XRD、荧光发射和激发光谱、余辉发射光谱与衰减曲线、色坐标和热释光谱测试手段对Y2O2S:Eu3+,Zn2+、Y2O2S:Eu3+,Ti4+、Y2O2S:Eu3+,Zn2+,Ti4+和Y2O2S:Eu3+,Mg2+,Ti4+进行了结构与性能的表征,发现其荧光发射与余辉发射基本一致,红色余辉发光主峰位于625 nm附近,来源于Eu3+的5D0→7F2跃迁发射。相比而言,Y2O2S:Eu3+,Zn2+,Ti4+余辉发光性能最好,可持续1.5 h左右。     

Spectroscopic properties of Er3+/Ho3+/Tm3+ doped α-SiAlON ceramics under 793 ​nm excitation

This paper reports the first demonstration of super broadband infrared downshifting emission extending from 1640 ​nm to 2200 ​nm with the full width at half maximum of ∼ 417 ​nm in lanthanides (Er³⁺, Ho³⁺, and Tm³⁺)-doped α-SiAlON ceramics upon 793 ​nm excitation. Using α-Si₃N₄ ceramic as a precursor the lanthanides-doped α-SiAlON ceramics were synthesized by the hot-press method. The lanthanides induced no significant secondary phases in the sintered α-SiAlON ceramics. Strong two-photon upconversion emission bands centered at 547, 671 and 694 ​nm have also been observed upon 793 ​nm excitation. The time-resolved measurements of the upconversion emissions confirm that the efficient energy transfer among the Er³⁺, Ho³⁺ and Tm³⁺ ions as well as the ground state absorption in Er³⁺ and Tm³⁺ are responsible for the observed spectroscopic properties.     

Ionization and dissociation of CH<Subscript>2</Subscript>I<Subscript>2</Subscript> and CH<Subscript>2</Subscript>ICl in femtosecond intense field

With the development of ultrafast laser technique,the femtosecond laser electric field is comparable to themolecular field experienced by valence electrons. In thiscase, the classical quantum mechanical theory, based onperturbation theory, becomes inapplicable. Theoreticalunderstanding of the interaction of molecules with intenselaser radiation is quite difficult. The Coulomb explosionhas been extensively studied[1—10] and explained by somesemiclassical models, such as the above threshold ion…     

Al3+掺杂NaGdF4:Er3+/Yb3+纳米晶上转换发光性能的研究

稀土离子掺杂的上转换纳米材料具有优异的光学性能,在光电等领域具有广阔的应用前景。本文采用溶剂热法,以乙二胺四乙酸(EDTA)为络合剂合成了的粗细均匀的六棱柱形的六方相Al3+掺杂NaGdF4:Er3+/Yb3+纳米棒。X射线研究表明适量的Al3+掺杂对NaGdF4的晶相没有产生影响,但使主衍射峰的位置发生偏移。在980nm激光激发下,与未掺杂的纳米晶相比,在Al3+的掺杂浓度为15%时,红绿光发光最大强度分别增强了5.7倍和5倍,且4F9 /2能级的荧光寿命被延长。Al3+掺杂对上转换发光的改善是因Er3+附近局部对称性的降低和粒子表面吸附基团的减少所致。